Processes for breaking petroleum emulsions



Patented Oct. 1 0,

PROCESSES BREAKING PETROLEUM EMULSIONS Melvin De Groote, UniversityCity, and Bernhard Keiser, Webster Groves, M0,, assignors to PetroliteCorporation, Ltd., Wilmington, DeL, a corporation of Delaware NoDrawing. Application June 26, 1948, Serial No. 35,524

11 Claims. 1

This invention relates to processes or procedures particularly adaptedfor preventing, break: ing or resolving emulsions of the water-in-oiltype, and particularly petroleum emulsions. This application is in parta continuation of our copending application Serial No. 666,822, filedMay 2, 1946, now abandoned.

Complementary to the above aspect of our invention is our companioninvention concerned with the new chemical products or compounds used asthe demulsifying agents in said aforementioned processes r procedures,as well as the application of such chemical compounds, products and thelike, in various other arts and industries, along with the method formanufacturing said new chemical products or compounds which are ofoutstanding value in demulsification. see our co-pending applicationSerial No. 35,525, filed June 26, 1948, which, in turn, is acontinuation of our co-pending application Seriial No. 758,489, filedJuly 1, 1947, now abandoned.

Our invention provides an economical and rapid process for resolvingpetroleum emulsions of the water-in-oil type that are commonly referredto as cut oil, roily oil, emulsified oil, etc., and which comprise finedroplets of naturally-occurring waters or brines dispersed in a more orless permanent state throughout the oil which constitutes the continuousphase of the emulsion.

It also provides an economical and rapid process for separatingemulsions which have been prepared under controlled conditions frommineral oil, such as crude oil and relatively soft waters or weakbrines. Controlled emulsification and subsequent demulsification underthe conditions just mentioned are of significant value in removingimpurities, particularly inorganic salts, from pipeline oil.

Demulsification, as contemplated in the present application, includesthe preventive step of commingling the demulsifier with the aqueouscomponent which would or might subsequently become either phase of theemulsion in the ab sence of such precautionary measure. similarly, suchdemulsifier may be mixed with the hydrocarbon component. Reference ismade to our pending applications Serial Nos. 8722 and 8723, both filedFebruary 16, 1948, now Patents Nos. 2,499,365 and 2,499,366, both datedMarch 7, 1950.

For the sake of convenience and in order to indicate with clarity therelationship between the compounds herein employed as demul'sifying'agents in relation to other compounds employed for the same purpose anddescribed incur last two mentioned co-pending applications, to wit,

Serial No. 8,722 and 8,723, reference is made to positions of the phenolis substituted ,by a hydrocarbon radical having 4 to 8 carbon atoms, thesubstantial absence of trifunctional phenols,- and aldehydes having notover 8 carbon atoms, subsequent oxyalkylation, and specificallyoxyeth'ylation, yields products of unusual value for demulsificationpurposes, provided' oxyalkylation is continued to the degree thathydrophile properties are imparted to the compound. By substantialabsence of trifunctional phenols, we mean that such materials may bepresent only in amounts so small that they do not interfere with theformation of a solvent-soluble resin product,

and especially, of a hydrophile oxyalkylated derivative thereof. Theactual amounts to be tol-i erated will, of course, vary with the naturof the other components of the system; but in gen-5 eral, the proportionof trifunctional' phenols which is tolerable in the conventionalresinification procedures illustrated herein is quite small. Inexperiments following conventional procedure using an acid catalyst inwhich we have included trifuncti'onal phenols in amounts of from 3%i'tcabout 1% or somewhat less, based on the dj;

functional phenols, we have encountered difiicul ties in preparingoxyalkylated derivativesof the I type useful in the practice of thisinvention. I

Such products are rarely asin'gle chemical compound; but arealmost'invariab1ya' mixture" of cogeners. One useful type 'of compoundmay; be exemplified in an idealized ,si1nplification* in' the followingformula: v

which, in turn, is considered a derivative of the l fusible, organicsolvent-soluble resin polymer OH I- H 0H H E Q 1 In these formulae n"represents a numera. varying from 1 to 13, or even more, provided theparent resin is fusible and organic solvent-soluble; n represents anumeral varying from 1 to 20, with the proviso that the average value ofn be at least 2; and R is a hydrocarbon radical having at least 4 andnot over 8 carbon atoms. These numerical values of n and n" are, ofcourse, on a statistical basis.

The demulsifying agents employed in the present process are similar tothose described in our last aforementioned co-pending application, towit, Serial No. 8,731, and are also obtained from solvent-soluble,fusible, phenol-aldehyde resins. The specific demulsifying agents hereinspecified are derived from phenols having a long chain meta substituentor the same type of phenol in combination with difunctional phenols, orin combination with trifunctional phenols free from a long chain metasubstituent, or in combination with both of these other types ofphenols.

Thus, in the simplest aspect in which oxyalkylated solvent-solublefusible resins are derived from a long chain meta substituted phenol,such as anacardol, dihydroanacardol, tetrahydroanacardol, side chainchlorinated cardanol, etc., the compound may be exemplified in anidealized simplication in the following formula:

igl R LO JTO which, in turn, is considered a derivative of the fusible,organic solvent-soluble, resin polymer nil In these formulae n"represents a numeral varying from 1 to 13, or even more, provided theparent resin is fusible and organic solvent-soluble; n represents anumeral varying from 1 to 20, with the proviso that the average value ofn be at least 2; and R, is a hydrocarbon radical, or a chlorinatedhydrocarbon radical having carbon atoms and derived from cashew nutshellliquid, with or without hydrogenation. These numerical values of 1L andn" are, of course, on a statistical basis.

The present invention involves the use as a demulsifier of a hydrophileoxyalkylated organic solvent-soluble fusible phenol-aldehyde resinderived from an aldehyde having not more than 8 carbon atoms and acashew nutshell liquid or a hydrogenated or chlorinated derivativethereof. Such resins may be obtained from such long chain metasubstituted phenols alone or in combination with difunctional phenols,or in combination with trifunctional phenols free from a long chain metaposition, or in combination with both such types. Such oxyalkylatedphenol-aldehyde resins owe their hydrophile property to the fact thatthe ratio of oxyalkylated groups to phenolic nuclei is at least 2 to 1,and with the further limitation that the alkylene radicals of theoxyalkylene groups are ethylene, propylene, butylene, hydroxypropylene,or hydroxybutylene, corresponding to the alpha-beta alkylene oxides,ethylene oxides, alpha-beta propylene oxides, alpha-beta butyleneoxides, glycide or methylglycide.

More particularly, the present invention in- 4 volves the use, as ademulsifier, of a compound having the following characteristics:

1) Essentially a polymer, probably linear but not necessarily so, havingat least 3 and preferably not over 15 or 20 phenolic or structuralunits. It may have more, as previously noted.

(2) The parent resin polymer being fusible and organic solvent-soluble,as hereinafter described.

(3) The parent resin polymer being free from cross-linking, or structurewhich cross-links during the heating incident to the oxyalkylationprocedure to an extent suflicient to prevent the possession ofhydrophile or sub-surface-active or surface-active properties by theoxyalkylated resin. Minor proportions of trifunctional phenols sometimespresent in commercial difunctional phenols are usually harmless.

(4) Each alkyleneoxy group is introduced at the phenolic hydroxylposition, except possibly in an exceptional instance, where a stablemethylol group has been formed by virtue of resin manu facture, inpresence of an alkaline catalyst. Such occurrence of a stable methylolradical is the exception, rather than the rule, and in any event,apparently does not occur when the resin is manufactured in the presenceof an acid catalyst.

(5) The total number of alkyleneoxy radicals introduced must be at leastequal to twice the phenolic muclei.

(6) The number of alkyleneoxy radicals introduced not only must meet theminimum of item (5) above, but must be sufficient to endow the productwith suflicient hydrophile property to have emulsifying properties, orbe self-emulsifiable, or self-dispersible, or the equivalent, ashereinafter described. The invention is concerned particularly with theuse, as a reactant, of sub-surface-active and surface-active compounds.

(7) The use of a product derived from cashew nutshell liquid, with orwithout hydrogenation, so that all or a significant proportion of thephenolic nuclei contain a meta substituted hydrocarbon side chain having15 carbon atoms.

We have found that the remarkable properties of the parent materials asdemulsifiers persist in derivatives which bear a simple geneticrelationship to the parent material, and in fact, to the ultimate resinpolymer, for instance, in the products obtained by reaction of theoxyalkylated compounds with low molal monocarboxy acids, high molalmonocarboxy acids, polycarboxy acids or their anhydrides, alpha-chloromonocarboxy acids, epichlorohydrin, etc. The derivatives also preferablymust be obtained from oxyalkylated products, Showing at least thenecessary hydrophile properties per se.

More specifically then, the new compounds herein described andparticularly for use as demulsifying agents, are obtained from cashewnutshell liquid, anacardol (3-penta-decadienylphenol), cardanol(dihydroanacardol or 3-p-entadecenylphenol), and hydrogenated cardanol(dihydrocardanol or tetrahydroanacardol or 3- pentadecylphenol).Commercially, these products appear on the market in one of threeforms-cardanol, cashew nutshell liquid, and hydrogenated cardanol.

The new compounds or compositions herein described are prepared from thephenolic compositions present in or derived from the oils extracted fromthe Anacardium genus of the Anacardiaceae family, Cashew nutshell liquidis de- 5 scribed as consisting of about 90% anacardic acid 0221 13203and about 10% of cardol, oaafiaaoi, with Very small fractionalpercentages of other materials. The generally accepted formula ofanacardic acid is COOH Pyrolytic distillation causes conversion intophenols.

Another derivative of cashew nutshell liquid in addition to thehydrogenated derivative, is the chlorinated anacardol and chlorinatedcardanol. For practical purposes, the principal constituent ofchlorinated cashew nutshell liquid is chlorinated cardanol. Chlorinationrefers to side chain chlorination only, and not to nuclear chlorination.The actual purpose of chlorination is well known and involves theaddition of approximately 25% of chlorine, by weight, so as to stretchany ethylene linkage. See U. S. Patent No. 2,399,735, dated May 7, 1946,to Harvey.

These reactive phenolic compounds are combined with suitable aldehydes,including formaldehyde and its isomers, acetaldehyde and higheraldehydes, such as butyraldeyde, heptaldehyde, cyclic aldehydes, such asbenzaldehyde, furfural, etc. Resins can be prepared in which part of thetreated cashew nutshell liquid or its derivatives, is replaced byanother trifunctional phenol, such as ordinary phenol (hydroxybenzene),metacresol, or similar derivatives, in which the ethyl or propyl groupappears in the meta position. Furthermore, these compounds, which mayalso be called anacardic acid phenols, may be combined with difunctionalphenol, such as orthocresol, para-cresol, para-ethylphenol,para-propylphenol, para-butylphenol, para-amylpheno-l, para-hexylphenol,para-isooctylphenol, orthophenolphenol, ortho-b'enzylphenol,para-benzylphenol, para-cyclohexylphenol, phenol-phenylolmethylmethane,etc. The effectiveness of the chemical compounds herein contemplated fornumerous purposes, appears to be largely directly related to the longcarbon atom chain of the anacardic acid phenol. As a result, it is onlynecessary to have one anacardic acid phenol in a polymer interrupted byphenols having other structures. For instance, we have preparedexcellent products, in which one mole of cardanol or its equivalent,such as hydrogenated cardanol, has been combined with 2, 3 or 4 moles oforthocresol, tertiary amylphenol, tertiary butylphenol, etc. Similarly,excellent compounds have been prepared, in which 5% to 25% of cardanolhas been replaced by ordinary phenol or metacresol, particularly ifacetaldehyde or higher aldehydes are employed. Similarly, compounds havebeen prepared involving, for example, mole or slightly more of cardanol,one-fourth. mole or slightly less of phenol, or metacresol, and mole ofa difunctional phenol, such as orthocresol, para-cresol,para-butylphenol, para-amylphenol, etc.

Any aldehyde capable of forming a methylol or a substituted methylolgroup and having not more than 8 carbon atoms is satisfactory, so longas it does not possess some other functional group or structure whichwill conflict with the resinification reaction, or with the subsequentoxyalkylation of the resin, but the use of formaldehyde, in its cheapestform of an aqueous solution, for the production of the resins, isparticularly advantageous. Solid polymers of formaldehyde are moreexpensive and higher aldehydes are both less reactive, and are moreexpensive. Furthermore, the higher aldehydes may undergo other reactionswhich are not desirable, thus introducing difficulties into theresinification step. Thus acetaldehyde, for example, may undergo analdol condensation, and it and most of the higher aldehydes enter intoself-resinification when treated with strong acids or alkalies. On theother hand, higher aldehydes frequently beneficially affect thesolubility and fusibility of a resin. This is illustrated, for example,by the different characteristics of the resin prepared frompara-tertiary amylphenol and formaldehyde, on one hand, and a comparableproduct prepared from the same phenolic reactant and heptaldehyde on theother hand. The former, as shown in certain subsequent examples, is ahard, brittle, solid, whereas, the latter is soft and tacky, obviouslyeasier to handle in the subsequent oxyalkylation procedure.

Cyclic aldehydes may be employed, particularly benzaldehyde. Theemployment of furfural requires careful control, for the reason that inaddition to its aldehydic function, furfural can form vinylcondensations, by virtue of its unsaturated structure. The production ofresins from furfural for use in preparing products for the presentprocess is most conveniently conducted with weak alkaline catalysts andoften with alkali metal carbonates. Useful aldehydes, in addition toformaldehyde, are acetaldehyde, propionic a1- dehyde, butyraldehyde,Z-ethylhexanal, ethylbutyraldehyde, heptaldehyde, and benzaldehyde,furfural and glyoxal. It would appear that the use of glyoxal shouldbeavoided, due to the fact that it is tetrafunctional. However,- ourexperience has been that, in resin manufacture and particularly asdescribed herein, apparently only one of the aldehydic functions entersinto the resinification reaction. The inability of the other aldehydicfunction to enter into the reaction is presumably due ,to sterichindrance. Needless to say, one can use a mixture of two or morealdehydes, although usually this has no advantage.

Resins of-the kind which are used as intermediates for the compoundsusedin the practice of this'i'nvention are obtained with the use of acidcatalysts or alkaline catalysts, or without the use of any catalyst atall. Amongfthe useful alkaline catalysts are ammonia, amines, and aquaternary ammonium bases. It is generally accepted that when ammoniaandaminesare em-.

ployed as catalysts, they enter into the condensation reaction, and, infact, may operate by initial combination with the aldehydic reactant.The compound hexamethylenetetramine illustrates such a combination. Inlight of these various reactions, it becomes difficult to presentanyformula which would depict the structure; of the various resins priorto oxyalkylation. More will be said subsequently as to the differencebetween the useof alkaline catalyst and an acid catalyst; even in theuse of an alkaline catalyst, there is considerable evidence to indicatethat the products are not identical where dilferent basicmaterials'are'emp-loyed. The basic materials employed include not onlythose previously enumerated, but also the hydroxides of the alkalimetals, :hydroxides of the alkaline earth metals, salts of strong basesand weak acids, such assodium.

acetate, etc.

dodecylphenol; octadecylphenol; eicosylphenol; para-doeicosylphenol; andparathe resins herein described and used as raw materials are obtainedby the use of certain other phenols in combination with the cashewnutshell liquid phenol. Difunctional phenols having only one carbon atomin the substituent group are limited to ortho and para-cresol. Thosehaving 2 to 3 carbon atoms are limited to ortho and para-ethylcresol,and ortho and para-propylphenol. Particularly suitable among thedifunctional phenols are those having 4 to 8 carbon atoms in thesubstituent radical. This particular subdivision of difunctional phenolsinclude paratertiary butylphenol; para-secondary butylphenol;para-tertiary amylphenol; para-secondary amylphenol; para-tertiaryhexylphenol; paraisooctylphenol, ortho-phenylphenol; para-phenylphenol;ortho-benzylphenol; para-benzylphenol; and para-cyclohexylphenol, andthe corresponding ortho-para substituted metacresols and 3,5-Xylenols.

'as many as 24 carbon atoms include the following: Para-nonylphenol;para-decylphenol; parapara-tetradecylphenol parapara menthylphenol;paratetraeicosylphenol. The comparable ortho derivatives or mixtures ofthe ortho derivatives and para derivatives may be employed.Trifunctional phenols having no side chains or short side chains :arelimited to phenol hydroxy benzene) and metacresol. As far as thedifunctional phenols are concerned and to the extent that they arederivatives of hydroxy benzene, it is to be noted that the analogousortho-para substituted metacresols and 3,5-xylenols may also beemployed, insofar that they are still difunctional phenols and themethyl group or groups in the meta position are without substantialeffect on the property of the resin. Trifunctional phenols exclude anyhaving 4 carbon atoms or more in the meta position substituent.

It has been previously pointed out that the resins employed as rawmaterials in the manufacture of the herein described compounds areobtained from anacardic acid phenols alone, or in combination withdifunctional phenols or trifunctional phenols, or both. No descriptionof trifunctional phenols is needed, and as to difunctional phenols,reference is made to the language used in our aforementioned co-pendingapplications Serial Nos. 8,722 and 8,723, both filed February 16, 1948.As to anacardic acid phenols, as herein described, one may convenientlyemploy the formula:

in which R represents a hydrocarbon radical or a chlorinated hydrocarbonradical, as exemplified by cashew nutshell liquid phenol, or itshydrogenated or chlorinated derivative.

The manufacture of organic solvent-soluble thermoplastic phenol-aldehyderesins is concerned largely with the manufacture of (a) resoles orNovolaks from trifunctional phenols; (b) manufacture of varnish resinsfrom difunctional phenols; and (c) the manufacture of the cardanol typeresin from phenols or phenolic mixtures, as previously specified. Thereis an ample description in the literature as to the manufacture ofresins from cardanol type phenols alone and in combination with otherphenols. An suitable process may be employed to make the hereindescribed resins which are used as raw materials. We have found it mostconvenient to use thesame general procedures which are applicable to themanufacture of resinsfrom difunctional phenols, particularly in whichthe substituent radical has 4 to 8 carbon atoms. This procedure isdescribed, for example, in the literature, and specific examplesincluded in our aforementioned copending application Serial No. 8,731,filed February 16, 1948.

Thermoplastic or fusible phenol-aldehyde resins are usually manufacturedfor the varnish trade and oil solubility is of prime importance. Forthis reason, the common reactants employed are butylated phenols,amylated phenols, phenylphenols, etc. The methods employed inmanufacturing such resins are similar to those employed in themanufacture of ordinary phenolformaldehyde resins, in that either anacid or alkaline catalyst is usually employed. The procedure usuallydiffers from that employed in the manufacture of ordinaryphenol-aldehyde resins, in that phenol, being water-soluble, reactsreadil with an aqueous aldehyde solution without further difficulty,while when a Water-insoluble phenol is employed, some modification isusually adopted to increase the interfacial surface and thus causereaction to take place. A common solvent is sometimes employed. Anotherprocedure employs rather severe agitation to create a large interracialarea. Once the reaction starts to a moderate degree, it is possible thatboth reactants are somewhat soluble in the partially reacted mass andassist in hastening the reaction. We have found it desirable to employ asmall proportion of an organic sulfo-acid as a catalyst, either alone oralong with a mineral acid like sulfuric or hydrochloric acid. Forexample, alkylated aromatic sulfonic acids are effectively employed.Since commercial forms of such acids are commonly their alkali salts, itis sometimes convenient to use a small quantity of such alkali salt,plus a small quantity of strong mineral acid, as shown in the examplesbelow. If desired, such organic sulfo-acids may be prepared in situ inthe phenol employed, by reacting concentrated sulfuric acid with a smallproportion of the phenol. In such cases where xylene is used as asolvent and concentrated sulfuric acid is employed, some sulfonation ofthe Xylene probably occurs to produce the sulfo-acid. Addition of asolvent such as Xylene is advantageous, as hereinafter described indetail. Another variation of procedure is to employ such organicsulfo-acids, in the form of their salts, in connection with analkali-catalyzed resinification procedure. Detailed examples areincluded subsequently.

Sometimes conventional resinfication procedure is employed, using eitheracid or alkaline catalysts to produce low-stage resins. Such resins maybe employed as such, or may be altered or converted into high-stageresins, or in any event, into resins of higher molecular Weight, byheating along with the employment of vacuum so as to split off water orformaldehyde, or both. Generally speaking, temperatures employed,particularly with vacuum, may be in the neighborhood of to 250 C., orthereabouts.

In the hereto appended claims there is specifiied, among other things,the resin polymer containing at least 3 phenolic nuclei. Such minimummolecular. size is most conveniently determined, as a rule, bycryoscopic method, using benzene, or some other suitable solvent, forinstance, one of those mentioned elsewhere herein as a solvent for suchresins. As a matter of fact, using the procedures herein described orany conventional resinification procedure, will yield products usuallyhaving definitely in excess of three nuclei. In other words, a resinhaving an average of 4, or 5 /2 nuclei per unit is apt to be formed as aminimum in resinfication, except under certain special conditions wheredimerization may occur.

However, if resins are prepared at substantially higher temperatures,substituting cymene, tetralin, etc., or some other suitable solventwhich boils or refluxes at a higher temperature, instead of xylene, insubsequent examples, and if one doubles or triples the amount ofcatalyst, doubles or triples the time of refluxing, uses a marked excessof formaldehyde or other aldehyde, then the average size of the resin isapt to be distinctly over the above values, for example, it may average7 to units. Sometimes the expression low-stage resin or low-stageintermediate is employed to mean a stage having 6 or '7 units or evenless. In the appended claims we have used low-stage to mean 3 to 7 unitsbased on average molecular weight.

The molecular weight determinations, of course, require that the productbe completely soluble in the particular solvent selected as, forinstance, benzene. The molecular weight determination of such solutionmay involve either the freezing point as in the cryoscopic method, or,less conveniently perhaps, the boiling point in an ebullioscopic method.The advantage of the ebullioscopic method is that, in comparison withthe cryoscopic method, it is more apt to insure complete solubility. Onesuch common method to employ is that of Menzies and Wright (see J. Am.Chem. Soc. 43, 2309 and 2314 (1921)). Any suitable method fordetermining molecular weights will serve, although almost any procedureadopted has inherent limitations. A good method for determining themolecular weights of resins, especially solvent-soluble resins, is thecryoscopic procedure of Krumbhaar which employs diphenylamine as asolvent (see Coating and Ink Resins, page 157, Reinhold Publishing Co.1947).

Subsequent examples will illustrate the use of an acid catalyst, analkaline catalyst, and no catalyst. As far as resin manufacture per seis concerned, we prefer to use an acid catalyst, and particularly amixture of an organic sulfo-acid and a mineral acid, along with asuitable solvent, such as xylene, as hereinafter illustrated in detail.However, we have obtained products from resins obtained by use of analkaline catalyst which were just as satisfactory as those obtainedemploying acid catalysts. Sometimes a combination of both types ofcatalysts is used in different stages of resinification. Resins soobtained are with the result that one obtains a resin havingapproximately double this molecular weight. The usual procedure is touse a secondarystep, heat-l ing the resin in the presence orabsence ofan inert gas, including steam, or by use of vacuum.

We have found that under the usual conditions of resinificationemploying .pheno sof the kind.

here described, there is littleor no tendency to formbinuclearcompounds, i. e., dimers, resulting from the combination, forexample,-of 2 moles'of a phenol and one mole of formaldehyde,particularly where the substituent has 4 or 5 carbon moles per mole ofaldehyde. droxydiphenylmethanes obtained fromsubstituted phenols are notresins as that term is used herein.

Although any conventional procedure ordinarily employed may be used inthe'manufactureof the herein contemplated resins or, for, that matter,such resins may be purchased in the open market, we have foundv itparticularly desirableto use the procedures described elsewhere herein,and employing a' combination of an organic sulfo-acid and a mineral acidas a catalyst, and

xylene as a solvent. Byway of illustration, cer,-;,j tain subsequentexamplesare included-but it to be understoodjthe herein described inventionis not concerned with the resins per se or with any particularmethod of manufacture but is concerned with the use of derivativesobtained,

by the subsequent oxyalkylation thereof. The

phenol-aldehyde resins may be prepared in any suitable manner.

Oxyalkylation, particularlyoxyethylation which is the preferredreaction, depends on contact between a non-gaseous phase and a gaseousphase. It can, for example. be carried out by melting the thermoplasticresin and subjecting it to treatment with ethylene oxide or the like, or

by treating a suitable solution or suspension. Since the melting pointsof the resins are often higher than desired in the initial stageofoxyethylation, we have found it advantageous to use a solution orsuspension of thermoplastic resin in an inert solvent such as xylene.Under such circumstances, the resin obtained in the usual'manner isdissolved by heating in xylene under a reflux condenseror in any othersuitable manner. r Since xylene or an equivalent inert solvent ispresent or may be present during oxyalkylation,

it is obvious there is no objection to having a I solvent present duringthe resinifying stage if, in;

addition to being inert towards the resin,;it is also inert towards thereactants and also inert towards water. Numerous solvents, particularlyof aromatic or cyclic nature, are suitably adapted for such use.Examples of such solvents arexylene,cymene, ethyl benzen'aipropylbenzene, mesitylene, decalin '(decahydronaphthalene) tetra:

lin (tetrahydronaphthalene), ethylene glycol diethylether, diethylene ;glycol"diethylether, and V tetraethy'lene" glycol dimethylether. V or,mixtures of one or more. Solventssuch as dichloroethyl ether, ordichloropropylether may be employed either alone or in mixture but havethe objection that the chlorine atom in/the compound'may slowly combinewith the alkaline catalyst em.- ployed in oxyethylation. "Suitablesolvents may 11 be selected from this group for molecular weightdeterminations.

The use of such solvents is a convenient expedient in the manufacture ofthe thermoplastic resins, particularly since the solvent gives a moreliquid reaction mass and thus prevents overheating, and also because thesolvent can be employed in connection with a reflux condenser and awater trap to assist in the removal of water of reaction and also waterpresent as part of the formaldehyde reactant when an aqueous solution offormaldehyde is used. Such aqueous solution, of course, with theordinary product of commerce containing about 37V;% to 40% formaldehyde,is the preferred reactant. When such solvent is used, it isadvantageously added at the beginning of the resinification procedure,or before the reaction has proceeded very far.

The solvent can be removed afterwards by distillation with or withoutthe use of vacuum, and a final higher temperature can be employed tocomplete reaction, if desired. In many instances, it is most desirableto permit part of the solvent, particularly when it is inexpensive, e.g., xylene, to remain behind in a predetermined amount, so as to have aresin which can be handled more conveniently in the oxyalkylation stage.If a more expensive solvent, such as decalin, is employed, xylene orother inexpensive solvent may be added after the removal of decalin, ifdesired.

Reference has been made to the word fusible." Ordinarily a thermoplasticresin is identified as one which can be heated repeatedly and still notlose its thermoplasticity. It is recognized, however, that one may havea resin which is initially thermoplastic, but on repeated heating, maybecome insoluble in an organic solvent, or at least no longerthermoplastic, due to the fact that certain changes take place veryslowly. As far as the present invention is concerned, it is obvious thata resin, to be suitable, need only be sufficiently fusible to permitprocessing to produce our oxyalkylated products and not yieldinsoluble's or cause insolubilization or gel formation, or rubberiness,as previously described. Thus, resins which are, strictly speaking,fusible but not necessarily thermoplastic in the most rigid sense thatsuch terminology would be applied to the mechanical properties of aresin, are useful intermediates. The bulk of all fusible resins of thekind herein described are thermoplastic.

The fusible or thermoplastic resins, or solven soluble resins, hereinemployed as reactants, are water-insoluble, or have no appreciablehydrophile properties. The hydrophile property is introduced byoxyalkylation. In the hereto appended claims and elsewhere theexpression water-insoluble is used to point out this characteristic ofthe resins used.

Previous reference has been made to organic solvent-soluble resins, suchs Novolaks or resoles of the kind obtained exclusively from difunctionalphenols. The present invention involves at least three types of resinswhich have been specified in detail. All these may be considered asmembers of the broad generic class of organic solvent-soluble fusiblephenol-aldehyde resins contemplated in our two aforementioned copendingapplications Serial Nos. 8,722 and 8,723. In all such instances, theresin consists of discrete or separate molecules, as differentiated froma completely cross-linked resin. Fusibility and solubility in an organicsolvent are characteristic of this state of sub-division.

The following examples, 1 through and ineluding 15 are derived fromcashew nutshell liquid phenols, or their derivatives alone; Examples 16through 33 inclusive, are concerned with examples where a trifunctionalphenol free from a long chain meta substituent is used in combination;Examples 34 through 59*, inclusive, are concerned with examples where adifunctional phenol is used in connection with the same type ofcompound; and 60 through 82 are concerned with compounds where all threetypes of phenolic compounds are employed:

EXAMPLE 1 Grams Cardanol (vacuum distilled) 403.2 Formaldehyde (37%)113.4 Xylene 403.2 Concentrated HCl 3.3

Monoalkyl (CID-C20, principally C12-C14) benzene monosulfonic acidsodium salt 1.4

(Examples of alkylaryl sulfonic acids which serve as catalysts and asemulsifiers particularly in the form of sodium salts include thefollowing:

R is an alkyl hydrocarbon radical having 12-14 carbon atoms.

R is an alkyl radical having 312 carbon atoms and 1:. represents thenumeral 3, 2, or 1, usually 2, in such instances where R contains lessthan 8 carbon atoms.

With respect to alkylaryl sulfonic acids or the sodium salts, we haveemployed a monoalkylated benzene monosulfonic acid or the sodium saltthereof, wherein the alkyl group contains 10 to 14 carbon atoms. We havefound equally effective and interchangeable the following specificsulfonic acids or their sodium salts; A mixture of diand tri-propylatednaphthalene monosulfonic acid; diamylated naphthalene monosulfonic acid;and nonyl naphthalene monosulfonic cid.)

The equipment used was a conventional twopiece laboratory resin pot. Thecover part of the equipment had four openings: one for reflux condenser;one for the stirring device; one for a separatory funnel or other meansof adding reactants; and a thermometer well. In the manipulationemployed, the separatory funnel insert for adding reactants was notused. The device was equipped with a combination reflux and watertrapapparatus so that the single piece of apparatus could be used as eithera refiux condenser or a water trap, depending upon the position of thethree-way glass stop-cock. This pemitted convenient withdrawal or waterfrom the water trap. The equipment, furthermore, pemitted any setting ofthe valve without disconnectin the equipment. The resin pot was heatedwith a glass fiber electrical heater constructed to fit snugly aroundthe resin pot. Such heaters, with regulators, are readily available.

The phenol-formaldehyde acid catalyst (acid and sulfonate salt incombination) and solvent were combined in the resin pot described. Thisparticular resin was a reddish-black liquid, having a viscositycomparable to that of ordinary oil or slightly in excess thereof. Heatwas applied with gentle stirring and the temperature was raised to -850., at which point a mild exol3 thermic reaction took place. Thisreaction raised the temperature to approximately l05-1l0 C. The reactionmixture was then permitted to reflux at 100-l05 C. for approximatelythree and a half hours. The reflux trap arrangement was then changedfrom the reflux position to the normal water entrapment position. Thewater of solution and the Water of reaction were permitted to distil outand collect in the trap. As the water distilled out, the temperaturegradually increased to approximately 150 C. which required between 1.5to 2 hours. At this point the water recovered in the trap, after makingallowance for a small amount of water held up in the solvent,corresponded to the expected quantity.

The solvent solution so obtained was used as such in subsequentoxyalkylation steps. We have also removed the solvent by conventionalmeans,

such as evaporation, distillation or vacuum distillation, and wecustomarily take a small sample of the solvent solution and evaporatethe solvent to note the characteristics of the'solvent-free resin. Thexylene-free resin obtained was reddish-black in color, and soft topliable in consistency.

EXAMPLE 2 Grams Cardanol (vacuum distilled) 576 Formaldehyde (37%) 160Ammonia (26 Baum or about 28%) 18.3

Xylene 575 All these items were mixed together and "refluxed for 6hours, followedbyremoval of water by distillation and heating to 125 C.for approximately 4 hours, forming a pliableor semi-solid resin. Thereactants were, of course,.stirred during the reflux period. The resinso obtained is thermoplastic and soluble-in xylene.

3 1 v Gram-s Cardanol (vacuum distilled) 44.7.0 Concentrated sulfuricacid 5;O Acetaldehyde 78.0 Xylene 200.0

The phenol, acid catalyst, and 50 grams of xylene were combined in theresin pot previously described under Example 1*. The initial mixture.

did not include the aldehyde- The'mixture was heated with stirring toapproximatelyl50 C. and permitted to reflux. I

The remainder of the Xylene-1 50 grams..was

then mixed with the acetaldehyde, and this mix- Th 'temperatureslowlydropped, as Water of reaction formed, to.

about 100 to 110 C., with the reflux temperature being determined by theboiling point of water. After all the aldehyde had-been added,

the reactants were permitted to refiuxfor -between an hour to an hourand a half before removing the water by means of the trap arrangement.After the water was removed, the re mainder of the procedure wasessentially the same as in Example 1*. The solvent-freeresinwasreddish-black in color and comparatively soft.

example (Example 4?). theamount :otxyleneimay In subsequent experimentswhere this pro cedure is followed or the modifications in'the next beincreased as the occasion requires. 'ilnder such circumstances, 50 gramsof xylene are-used in the initial step and the residual xylene, whichmay be more than 150 grams, is added in the second stage.

EXAMPLE 4 v Grams Cardanol (vacuum distilled) .288 n-ButyraldehydeConcentrated sulfuric acid 3 Xylene 200 The procedure employed wasessentially the same'as in Example 3 where acetaldehyde was employed,but with the difference that, due to the fact that theparticularaldehyde was a higher boiling al dehyde,,it was not necessary to diluteit with xylene, although this procedure'imay be employed, if desired.For this reason, we added all the xylene to the initial mixture and thehigher boiling aldehyde was added by means of the separatory funnelarrangement; thus, the phenol, acid catalyst and solvent combined in theresin pot by the same procedure used as in Example."

3 The solvent-free resin was soft and dark red in appearance. See whatis saidunder the preceding heading in regard to subsequent examples, ifmore than 200 grams of xyleneare employed.

EXAMPLE 5 I GIBJIIS Cardanol (vacuum distilled) 2880 Heptaldehyde 1140Concentrated sulfuric acid 30 Xylene 2000 Theiprocedure followed was-thesame as that of Example 4 The appearance of the solventa The phenolemployed was the product offered v for sale in the open market.

It was a brown mealy solid, suggestive in appearance of ofi-color brownsugar. Hydrogenated cardanol is -hy-' drogenated in the side chain only.Theapp'aratus employed was that describe-d in Example 1*, preceding. 1 If All of the above ingredients; except the. xylene, were mixed, and,withstrong agitation, are heated slowly toapproximately 65 C. when'asp'on taneous or vigorous reaction takes place so as to raise thetemperature rather rapidly to C.,

accompanied by some foaming. At this point the 2000 grams .of xylene-are.addedto vthi-n'out the reactionmixture and permitsatisfactoryagitation. .fIhe mixture is allowed to disti'l under 'a reflux condenserwith the temperature deter-' mined by boiling point of water,approximately C. Operatingjtemperature is usually within the range of toC. After the completion of a z hour'reflux distillation at thistemperature,

or at least sufficient .to eliminate any odor offormaldehyde, removal ofthe water is started,

Approxiusing the usual trap arrangement. mately '685 grams of water aredistilled off. "The product, minus the solvent, is a semi-solid, tackyresin of a heavy tar-like consistency. It is decidedly-more viscous thansimilar resins "made 15 from cardanol which has not been subjected tohydrogenation.

EXAMPLE '7 The same procedure was followed as in Example 3*, except thatthe cardanol was replaced, mole for mole, with hydrogenated cardanol.The resin obtained is somewhat softer and more fluid in character thanthe comparable resin obtained from formaldehyde.

EXAMPLE 8 The same procedure was followed as in Example 4 except thatthe acetaldehyde was replaced, mole for mole, with n-butyraldehyde. Theresin obtained was somewhat softer and more fluid in character than thecomparable resin obtained from formaldehyde.

EXAMPLE 9 The same procedure was followed as in Example 4 except thatthe acetaldehyde was replaced, mole for mole, with heptaldehyde. Theresin obtained was somewhat softer and more fluid in character than thecomparable resin obtained from formaldehyde.

Previous reference has been made to chlorinated cardanol. Laboratorybatches can be prepared conveniently, following the procedure which weuse and which is as follows: 1500 grams of vacuum distilled cardanol arechlorinated with stirring for 10 hours between and 60 C. The amount ofchlorine absorbed is about 23% of the cardanol. The chlorinatedsubstance is a thick, viscous black tar.

EXAMPLE 10 Grams Chlorinated cardanol 342 Butyraldehyde 72 Concentratedsulfuric acid 4 Xylene 350 The same procedure was followed as in Example4 preceding. The reflux time was 1 hours. The resin, minus solvents, wasblack and semisoft in appearance. The solution as prepared contained46.8% xylene.

EXAMPLE 1 1 Grams Hydrogenated cardanol 288 Propionic aldehyde (96%) 61Concentrated sulfuric acid A 4.5

Xylene 250 The same procedure was employed as in Example l preceding.The solvent-free resin was reddish black in color and soft to semi-fluidin consistency. The xylene solution as prepared contained &3.2% xylene.

EXAMPLE 12 Grams Cardanol (vacuum distilled) 432 Benzaldehyde 159Concentrated sulfuric acid 6 Xylene 300 The procedure followed was thesame as described in Example 4 preceding. The appearance of the resinwas somewhat suggestive of rubberiness and it was not entirelyhomogeneous. It was dark reddish-brown in color.

EXAMPLE 13 Grams Cardanol (vacuum distilled) 576 Furfural 192 Potassiumcarbonate 12 The furfural was shaken with dry sodium carbonate prior touse, to eliminate any acids, etc. The procedure employed wassubstantially that described in detail in Technical Bulletin, No. 109,of the Quaker Oats Co., Chicago, Ill. The above reactants were heatedunder the reflux condenser for 2 hours in the same resin pot arrangementdescribed in Example 1*. The separatory funnel device was not employed.No xylene or other solvent was added at this stage. The amount ofmaterial vaporized and condensed was comparatively small, except for thewater of reaction. At the end of this heating or reflux period the trapwas set to remove the water. The maximum temperature during and afterremoval of water was approximately 202 C. The material in the traprepresented 32 cc. water and 2.5 cc. furfural. At this point 250 gramsof xylene were added so as to give a suitable solution. The resin wasreddish-black in color, xylene-soluble and semi-soft or tacky inconsistency. The solution as prepared contained approximately 25%xylene.

EXAMPLE 14 A resin was prepared in the exact manner described underExample 5*. The resin so obtained was subjected to vacuum distillationin the following manner: The xylene solution was heated to 200 C. undervacuum (25 mm. Hg). This vacuum distillation removed all the solvent andresulted in a reddish-black resin which was somewhat more viscous thanthe same resin obtained by evaporation of the xylene on a steam bathovernight. The appearance of the resin so obtained was reddish-black incolor, and it was, of course, xylene-soluble.

EXAMPLE 15 Grams Cardanol (vacuum distilled) 576 Formaldehyde (37 178Xylene 300 Catalyst None The above ingredients were placed in anautoclave with a stirrer and heated to approximately 160 C., and stirredfor 4 hours. The pressure during this time varied from to pounds persquare inch gauge pressure. The resultant product was a thick reddishmaterial, having somewhat gummy or rubbery characteristics. To this wereadded 1000 grams of xylene and heated for an hour at C. under pressureof 100 pounds per square inch so as to give a complete solution. Thissolution was then treated in the following manner: The solution wasdiluted further by the addition of 2100 grams of xylene. This dilutexylene solution was divided into three parts, and each third handledseparately. The procedure was simply to wash approximately three timeswith an equal volume of water and then remove the xylene under 15 mm.(Hg) pressure until the xylene was 63%. This solution was a brownviscous syrup, which was subsequently subjected to oxyalkylation. Theresin, when separated from the solvent was a reddish-amber semi-rubberymaterial.

EXAMPLE 16 Grams Cardanol (vacuum distilled) 245 Phenol 14.1Formaldehyde (37%) 80 Concentrated HCl 1 Monoalkyl (Cm-C20, principallyC12-C14) benzene monosulfonic acid sodium salt 1 Thea pparatus used wasthe same equipment, as described under the heading of Example 1. Theabove materials were mixed and heated with agitation for about 2 hoursat 100 C. or until there was no further odor of unreacted formalde hyde.After this, water was allowed to distilloff until the product began tothicken and then 200 grams of xylene were added so as to thin it. Themass was then allowed to reflux with the conventional trap whichseparated the water-and returned the condensed xylene. During theflnalstage, the temperature remained at approximately 140-150 C. The xylenewas then removed under vacuum, using a temperature of 160 C. The finalproduct was a semi-solid, tar -like resin, which was xylene-soluble.

EXAMPLE 17' j Grams Cardanol (vacuum distilled) 550 Phenol 26Formaldehyde (37%) 160- Ammonia (26 Baum or about 28%). 18.3

All items were mixed together and refluxed for 6 hours, followed byremoval of water by distillation, heated to 125 C. and held at thistemperature for approximately 4 hours, forming a semisolid or pliableresin. The resin so obtained was thermoplastic and soluble in xylene.

EXAMPLE 18 Grams Cardanol (vacuum distilled) 202 Phenol 28.2Concentrated sulfuric acid 3 Acetaldehyde 44 Xylene 350 The sameprocedure was followed as in the preceding example, that is, Example18*, except that the amounts of card'anol and phenol employed were 347grams and 100 grains, respectively. The solvent-free resin was soft anddark red in appearance.

EXAMPLE 20 The same procedure was followed as in Example 18 except thatthe amounts of cardanol and phenol employed Were 300 grams and 147grams, respectively. The resin obtained was soft.

EXAMPLE 21- Grams Cardanol (vacuum distilled) 250 Phenol 38vn-Butyraldehyde 72 Concentrated sulfuric acid 3 Xylene '200 Theprocedure employed was that of Example 4*. The resin was soft.

EXAMPLE 22 Grams Cardanol (vacuum distilled) 200 Phenol 88n-Butyraldehyde 72, Concentrated sulfuric acid 3 Xylene 20b The p oce ure ov as t s Example The procedure employed was that of; Example l fTheresin was soft. V p

" EXAMPLE24$- forms- I The procedure employed is that of Example 4Theresin is soft.

EXAMPLE 25 Hydrogenated Cardanol 2 Phenol Formaldehyde (37%)Concentrated HCl l; 1 Monoalkyl (Cm-C20) principally C12C14-) benzenemonosulfonic acid. sodium salt l Xylene 200 The procedure followedwasthat of Exampleli The product minus the solvent was a semi-solid, tackyresin of a heavy tar-like consistency. .It

was decidedly more; viscous than similar; resins madefrom cardanol';which has-not been subi .iectedlto'hydrogenation. y I v K MP' E The sameprocedurewas followed-as in.

,amples 16 to 25*, except that phenol was re g 7 placed by the molarequivalent, of 'metacresol. The products were similar to those obtainedwith the use ofphenol. 1

" EXAMPLE 2'7 The same procedure was followed as in Ex-] amples 16 to 25except that phenol is replaced by the molar equivalent ofmetaethylphenol or Xylene 30 0- The procedure followed was the same asExample 1 preceding. The-resin minus "'sol vents] was reddish-black incolor; and semipliable tb hardiin consistency. The solution prepared coitained 48.7 xylene.

Grams A aide- 19889 19 The procedure employed was the'same asdescribedin Example 4 preceding- The sol-ventfree resin was black and soft tosemi-fluid in consistency. The solution as prepared conain d. ,3- yleniepm dure followed, was h a as scribed in Example 45, preceding. Thesolventfree resin was reddish-black in color, xylenesoluble andsemi-soft to pliable in consistency.

, EXAMPLE 31 Grams Cardanol (vacuum distilled) 490 Metacresol 32.4Furfural 192 Potassium carbonate 12 The procedure followed wasidentically the same as in Example 13 preceding, with the addition of250 grams of xylene. The solvent-free resin was reddish-black in color,xylene-soluble, semi-hard or pliable in consistency, with sometackiness. The solution, as prepared, contained 27% xylene.

EXAM'PLE 32 A resin was prepared in the same manner as described underExample 23 The resin so obtained was subjected tovacuum distillation inthe following manner: The xylene was removed by subjecting the solutionto heat and vacuum, using a temperature up to 200 C; and a vacuum of 25mm. Hg. As a result of such treatment, the xylene was removed completelyand the resin so obtained was more viscous than the one which had notbeen heated and where xylene had been removed by evaporation on a steambath overnight. The appearance of the resin was not changed materiallyas it was still reddish-black in color and was still xylene-soluble.

EXAMPLE 33 Grams Cardanol (vacuum distilled) 518 Metacresol 21.6Diamylphenol 70.2 Formaldehyde (37%) 203 Catalyst None Xylene 450 Theabove mixture was placed in an autoclave and heated for 4% hours at 150to 172 C. During this time the gauge pressure varied from 120 lbs. persquare inch to 170 pounds per square inch. The resultant product was asomewhat viscous, reddish mixture. To this there was added 875 grams ofxylene and heated for one hour at 158-165 C. under a pressure of 100pounds per square inch, so as to give a completely homogeneous solution.This solution was treated in the following manner: It was dilutedfurther with the addition of 2000 grams of xylene. This dilute xylenesolution was divided into three parts and each third handled separately.The procedure was simply to wash approximately three times with an equalvolume of water and remove the xylene under 25 mm.

20 Hg: pressure until the xylene represented about 43% ofthe solution.This was a viscous, red dish-black mixture, which was subsequentlysubjected to oxyalkylation' The resin, when separated from the solvent,was reddish-black in color and semi-pliable to tacky in consistency.

EXAMPLE 34 Y a V Grams Cardanol (vacuum distilled); 576 Paracresol 108Formaldehyde (37%), 240 Concentrated I-ICl 4.5 Xylene 25o Monoalkyl (C-C20, principally 012-014) benzene monosulfonic acid sodium salt" 3 Theequipment usedwas the same a described in Example 1 The procedurefollowed was that of Example 16 except that during the final stage, thetemperature remained at approximately C, The xylene was then removedunder vacuum (approximately 25 mm. Hg), using a temperature of C. Thefinal product was a soft, pliable resin which was xylene-soluble.

EXAMPLE 35 Grams Cardanol 576 Paracresol -Q L 108 Formaldehyde (37%)"240 Ammonia (26 Baum) 27.5

All of the above materials were refluxed together for 6 hours, followedby removal of water .by distillation, heated to 125'"'C."and' held atthis temperature for approximately 4 hours until a hard, brittle resinwas'obtained. The resin so obtained was thermoplastic and soluble inxylene.

EXAMPLE 36E The procedure followed was the same as that described inExample 3 preceding. The solventfree resin obtained was soft, almostfluid, and xylene-soluble.

EXAMPLE 37 The same procedure was followed as in Example 36*, exceptthat the amount of cardanol employed was reduced to 268.2 grams and theamount of cresol was increased to 178.8 grams.

EXAMPLE 38 The same procedure was followed as in Example 36, except thatthe amount of cardanol employed was reduced to 137 .3 grams and theamount of cresol increased to 268 grams.

EXAMPLE 39 The same procedurewas followed as in Example 36, except thatpara-ethylphenol, para-propylphenol, para-butylphenol, para-amylphenol,or para-octylphenol was substituted in molar equivalent amounts for theortho or para-cresol.

EXAMPLE 40 Thesame procedure was followed as in the preceding-sixexamples, except that 78 grams of acetaldehyde-were replaced by amolar equivalent of normal-butyra1dehyde.--

21 EXAMPLE 41 The same procedure was followed as in Examples 36 to 38except that the '78 grams of acetaldehyde were replaced by a molarequivalent of heptaldehyde.

EXAMPLE 42 Grams Cardanol (vacuum distilled) 115.2 Para-ethylphenol 12.2Formaldehyde (37%) 40 Concentrated HCl .8 Monoalkyl (Cw-C20, principallyCiz-Cm) benzene monosulfonic acid sodium salt .5

Xylene 75 The molar ratio was 4 of cardanol to'l of paraethylphenol. Theprocedure followed was the same as that in Example 1.

EXAMPLE 43 The same procedure was followed as in the preceding example,except that the para-ethylphenol was replaced by the molar equivalentamount of ortho-cresol, para-butylphenol, para-octylphenol,para-amylphenol, para-phenylphenol, or other difunctional phenol. In thecorresponding example referred to in the subsequent table givingoxyethylation procedure, the specific phenol employed was para-secondarybutylphenol.

EXAlVIPLE 44 The same procedure was followed as in Example 42 andExample 43 except that the molar ratio of cardanol to difunctionalphenol was changed from 4 to 1 to 3 to 2 with the molar proportion oftotal phenol the same. Otherwise, the same reactants and the sameprocedures were employed. In the corresponding example referred to inthe subsequent table giving oxyethylation procedure, the specific phenolemployed was parasecondary butylphenol.

EXAMPLE 45 Examples 34 to 44 were repeated, replacing cardanol byhydrogenated cardanol. Since the commercial products are not one hundredpercent pure, it was not necessary to make any change in theformulations, because of the slight difference in molecular weightbetween hydrogenated cardanol and cardanol. However, allowance for thisslight difference can be made.

EXAMPLE 46 Grams Chlorinated cardanol 171 Para-tertiary amylphenol 82Butyraldehyde 72 Concentrated sulfuric acid 25 Xylene 250 The procedurefollowed was the same as described under the heading of Example 4*,preceding. The solvent-free resin was black and soft to semi-fluid inconsistency. The solution as prepared contained 44.8% xylene.

EXAMPLE 47 l V Grams Cardanol (vacuum distilled) a 288 Nonylphenol 220Butyraldehyde -1 144 Concentrated sulfuric acid Xylene 250 The procedurefollowed was the same as described under the heading of Example 4preceding. The solvent-free resin, was reddish-black 22* in color andsoft to semi-fiuid' in consistency; The solution, as prepared, contained29.4 xylene.

EXAMPLE 48 Grams Cardan'ol (vacuum distilled) 288 Menthylphenol 232Heptaldehyde 228 Concentrated sulfuric acid 8 Xylene 350 The procedurefollowed was the same as described under the heading of Examplelpreceding." The solvent-free resin was reddish-black in color and softto semi-fluid in consistency.

EXAMPLE 49 Cardanol (vacuum distilled) 288 Para-decylphenol 232'Butyraldehyde p 144 Concentrated sulfuric acid 5 Xylene 250 Theprocedure followed was the same as described under the heading ofExample 4 ,.preceding. The resultant solvent-free resin was semi-fluidand dark red'in appearance.

EXAMPLE 50 Grams Cardanol (vacuum distilled) 288 Nonylphenol 220-Benzaldehyde 2 12 Concentrated sulfuric aoid-- 4 Xylene 300 Theprocedure followed was the same as described under Example 4*,preceding. The resultant resin was dark red in color, and viscous inconsistency.

EXAMPLE 5-H Grams Cardanol (vacuum distilled) 288 Nonylphenol 220Furfural 192 Potassium carbonate 12 The'p-rooedure followed was the sameas in Example 13 preceding, including ,the addition of 250 grams ofxylene. The solvent-free resin was reddish-black in color,xylene-soluble, and semi-soft or tacky in consistency. The solution asprepared contained 27.4% xylene.

EXAMPLE 52 Cardanol (vacuum distilled) "[288 Nonylphenol 220Formaldehyde (37%) 1'76 Water 34 Xylene 226 Sodiumhydroxide 7.9

sodium acetate, Or acetic acid. The xylenesolu--- tion was heated undera condenser at C. for" Since subsequent experimentation llplwedihet smsyele his x lene at th s ra e so minutes.

I Grams.

- Grams ticular temperature employing vacuum tended to cause the productto become rubbery, the procedure employed was to permit the xylene toremain and add enough additional xylene so the final resin solutionrepresented 50%, by weight, of resin. The amount of xylene required was300 grams.

EXAMPLE 53 Grams Cardanol (vacuum distilled) 288 Nonylphenol 220Formaldehyde (37%) 1'78 Xylene 300 No catalyst None The same procedurewas followed as in Example 15 preceding. Reaction was conducted in astirring autoclave for 4 /2 hours at a temperature of 160 C. and 145pounds gauge pressure. When resinification was complete, 100 grams ofxylene were added and stirred, using the same temperature and pressurefor approximately one hour to obtain complete solution or suspension.The resin was dispersible in xylene but not clearly soluble.

It was clearly soluble, however, in diethylene gly- ,l

col diethylether. The solvent-free resin was reddish-amber in color andsemi-pliable to rubbery in consistency.

EXAMPLE 54 Grams Cardanol (vacuum distilled) 288 Decylphenol (para) 232Formaldehyde (37%) 1'78 Concentrated HCl 3.5 Xylene 300 Monoalkyl(Clo-C20, principally C12-C14) benzene monosulfonic acid sodium salt 1.8

The procedure followed was the same as described in the precedingExample 1*. The resin obtained was reddish-amber in color and semifiuidin consistency.

EXAIVIPLE 55 EXAMPLE 56 Grams Cardanol (vacuum distilled) 288Methylphenol 232 Acetaldehyde 88 Concentrated sulfuric acid 5 Xylene 100The procedure followed was the same as described under the heading ofExample 3*, preceding. The resin obtained was dark red, and soft tosemi-tacky in consistency.

EXAMPLE 5'7 Grams Cardanol (vacuum distilled) 288 Methylphenol 232Butyraldehyde 144 Concentrated sulfuric acid 5 Xylene 100 24 Theprocedure followed was the same as described under the heading ofExample 4*, preceding. The resin was dark red in color and soft to fluidin consistency. The final solution contained 13.5% xylene.

EXAlVIPLE 58 Grams Cardanol (vacuum distilled) 230 Para-phenylphenol 34Formaldehyde Concentrated HCl 1 Monoalkyl (Cm-C20, principally C12C14)benbene monosulfonic acid sodium salt 1 Xylene 150 The procedurefollowed was the same as described in Example 1*, preceding. Thesolventfree resin was dark red or reddish-brown in color, semi-solid andsomewhat pliable, but was dispersible in xylene but not completelysoluble. The

solution as prepared'contained 35% xylene.

EXAMPLE 59 Grams Hydrogenated cardanol 144 Amylphenol 164 Formaldehyde(37%) 120 Concentrated I-ICl 2.5

Monoalkyl (Cm-C20, principally C12-C14) benzene monosulfonic acid sodiumsalt 1.5 Xylene 250 The procedure followed was that described in Example1*, preceding. The resin obtained was a hard, brittle product,xylene-soluble. The solvent-free resin had a melting point of 105 C. Theresin as prepared contained 43% xylene.

EXAMPLE 60 Grams Cardanol (vacuum distilled) 576 Paracresol 54 Phenol 47Formaldehyde (37%) 240 Concentrated HCl 4.5 Monoalkyl (Cm-C20,principally 012-014) benzene sulfonic acid sodium salt 3 The sameequipment and the same procedure was followed as in Example 1 preceding.The resin was soft and pliable in consistency and xylene-soluble.

EXAMPLE 61 Grams Cardanol (vacuum distilled) 144 Para-nonylphenol 264Metacresol 32.4 Formaldehyde (37 162 Ammonia (26 Baum orabout 28%) 21Xylene 350 The procedure employed Was the same as described underExample 2 preceding.

EXAMPLE 62 Grams Cardanol (vacuum distilled) 288 Ortho or para-cresol 27Metacresol 27 Concentrated sulfuric acid 3 Acetaldehyde 66 Xylene Theprocedure followed was the same as in Example 5*, except that theresidual xylene added was 50 grams instead of 150, for the reason thatthe total amount of xylene was 100 grams instead of 200. The final resinwas soft, almost aeaasae 25 fluid, soluble in xylene and otherconventional solvents.

EXAMPLE 63 The same procedure. was followed as in Example 62 except theamount of cardanol employed was reduced to 268.2 grams and the amount ofcresol increased to 178.8 grams, of which /3 was metacresol and ortho orpara-cresol, .or a mixture thereof.

EXAMPLE 64 The same procedure was followed as. in Example 62 except thatthe amount of cardanol employed was reduced to 137,3 grams and theamount of cresol increased to 268.0 grams, of which /3 was metacresoland ortho or paracresol, or a mixture thereof.

EXAMPLE 65 The same procedure was followed asin Examples 62 63 and 7,except that para-ethylphenol, para-propylphenol, para-butylphenol,para-amylphenol, or para-octylphenol was substituted in molar equivalentamounts for the ortho'or paracresol.

. Grams Cardanol 288 Para-ethylphenol hl, 35.5 Phenol 23.5

Acetaldehyde 66 Concentrated sulfuric acid 3 Xylene 100.

The procedure followed was the same as that described in Example 3 withthe change in the amount of residual xylene added so as to conform toExample 58.

EXAMPLE 6'? Grams Cardanol (vacuum distilled) 288 Para-tertiarybutylphenol 37.5. Phenol 23.5 Concentrated sulfuric acid 3. Acetaldehyde6.6

Xylene 100 The procedure followed was the same as "that described inExample 3, with the change in "the amount of residual xylene added so asto conform to Example 58**. The final product was a soft, amber-coloredresin.

The same procedure as in the two preceding examples, but with the use ofnormal but'yraldehyde and normal heptaldehyde in molar quantities toreplace the acetaldehyde, gives, resulting resins of the same generalappearance.

EXAMPLE o8 Grams Cardanol 86.4

Phenol 9.4 Para-ethylphenol 12.2 Formaldehyde (37%) 40.6 ConcentratedH01 .8 Monoalkyl (Clo-C20, principally Clix-C14) benzene monosulfonicacid sodium salt .5 Xylene 100 The procedure followed was the. same asthat in Example 1*. v

EXAMPLE 69 The same procedure was followed as in the preceding example,except that the para-ethylphe- 26 1101 was replaced. by the equivalentmolar amount of para-propylphenol, para-butylphenol, para. octylphenol.paraamylphenol, para-phenylphea nol, or other difunctional phenol.Further variants include the replacement of :the phenol by a molarequivalent amount of metacresol or other low alkyl phenol, for instance,ethyl or propylphenol, providing the alkyl group is in the metaposition. 1

EXAMPLE 70a The same procedure was followed as in Exam ples 68 and 69except that the molal ratio of cardanol to the other phenols(difunctional and trifunctional phenols) was changed from &.to 2, to 2to 2 withthe samemolar proportionof total phenols. Otherwise, the. same.reactants and.

same procedures. were errmloyed.

EXAMPLE 71 hfsame procedure was followed as in Examples 'fi8 and 69except that the molal ratio of cardanol to the other phenols('d'ifunctional and trifunctional phenols) was changed from; 3 toT-2 to"2 to 3, with the same molar proportion-of total phenols. Otherwise,the'same reactants; and same procedures were employed.

The procedure followed was the same as in Ex ample 1 The resulting resinwas semi-"solid, tacky, and of heavytar like consistency.

EX M L '7 w Examples 60 amen, preceding, wererepeated, replacing-cardanol by hydrogenated cardanol; Since the commercial product was notpure, it was not necessary to makeany change in proportions because ofthe slight difference in molecular weight between hydrogenated cardanoland cardanol. However, allowance for this slight'increase can be made. i

EXAMPLE. 74

V Grams Chlorinated cardanol 171 Menthylphenol 116 Metacresol 19Butyraldehyde 84.5

The procedure employed was the same as described under the=headingofExample 4, preceding-. 'Ihe resin obtain-edwas black in appearance andsoft tov semi pliable in consistency. The solution as prepared contained14.6% xylene.

EXAMPLE '15 I Gram Cardanol (vacuum distilled) Nonylphenol 33 Metacresol8.1 Formaldehyde (37%) 203 Catalyst None Xylene -J. 450

The procedure followed was substantially the same as described underExamples 15 and 33 preceding. The solvent-free resin was reddishblack incolor and soft to semi-pliable in consistency. The final solutioncontained 55% xylene.

EXAlVIPLE '76 Grams Cardanol (vacuum distilled) 144 Butylphenol '75Metacresol 19 Butyraldehyde 84.5 Concentrated sulfuric acid 3.5 Xylene200 The procedure employed was the same as described under the headingof Example 4*, preceding. The resin was reddish-black in color andsemi-fluid to pliable in consistency.

EXAMPLE 77 Grams Cardanol (vacuum distilled) 144 Para-octylphenol 103Metacresol 19 Butyraldehyde 84.5 Concentrated sulfuric acid 4.0

Xylene 225 The procedure employed was that described under the headingof Example 4 preceding. The resin was reddish-black in color andsemi-soft to pliable in consistency.

EXAMPLE 78 Grams Cardanol (vacuum distilled) 144 Metacresol 19Nonylphenol 110 Butyraldehyde 84.5 Concentrated sulfuric acid 4.0 Xylene250 The procedure followed was the same as described under the headingof Example 4*, preceding. The solVent-free resin was soft to semitackyin appearance and reddish-black in color. The solution as preparedcontained 42.5% xylene.

EXAMPLE '79 I Grams Cardanol (vacuum distilled) 245 Nonylphenol 187Metacresol 32.4 Furfural 192 Potassium carbonate 12 The procedurefollowed was the same as in Example 13*, preceding, including theaddition ff250, grams of xylene. The solvent-free resin wasreddish-black in color, xylene-soluble and semi-hard to pliable, withsome tackiness in its consistency. The solution as prepared contained28% xylene.

EXAIVIPLE 80 Grams Cardanol (vacuum distilled) 245 Menthylphenol 197Metacresol 32.4 Heptaldehyde 228 Concentrated sulfuric acid 8 Xylene 350The procedure followed was the same as described under the heading ofExample 4, preceding. The resin was reddish-amber in color and veryviscous or almost suggestive of a so id.

28 EXAMPLE 81 The resin was prepared in the manner described underExample preceding. Such resin was subjected to vacuum distillation inthe following manner: The maximum temperature employed was 204 C. at avacuum f 25 mm. (Hg). Under this stripping procedure all the xylene wasremoved and the resin obtained was reddish-black in color. It wasextremely tacky and decidedly more viscous or more nearly solid than theresin prior to vacuum distillation. It was, of course, xylene-soluble.

EXAMPLE 82 Grams Cardanol (vacuum distilled) 223 Ethylphenol 35.5 Phenol23.5 Concentrated sulfuric acid 3.0 Acetaldehyde 6.0

Xylene The procedure employed was that described under Example 3preceding. The resin was dark to reddish-black in appearance, semi-solidin consistency, and the solution as prepared contained 20% xylene.

EXAMPLE 83 Grams Cardanol (vacuum distilled) 144 Nonylphenol ,220Metacresol 28.5

Benzaldehyde 187 Concentrated sulfuric acid 4.5 Xylene 350 The procedureemployed was that described under the heading of Example 4 preceding.

The solvent-free resin was reddish-black in color and semi-soft topliable in consistency. The resin as prepared contained 38.9% xylene.

Monofunctional phenols, such as monofunctional diamylphenol, do notyield resins by reaction with formaldehyde, for the simple rea-. sonthat using conventional procedure one obtains a dimer consisting of twophenolic nuclei joined by methylene or a substituted methylene bridge.On the other hand, where the phenolic reactants are trifunctional, theaddition of moderate amounts of a monofunctional phenol tends to preventor reduce cross-linking, and thus insures the formationof a fusiblesolvent-soluble resin, i. e., a product which is a resin in the sensethat it contains three or morephenolic nuclei and is still sufiicientlyfree from cross-linking to represent discrete particles. Note the use ofmonofunctional :diamylphenol in certain of the preceding examples.

As far as themanufacture of resins is concerned, it is usuall mostconvenient to employ a catalyst such as illustrated by previousexamples.

Previous reference has been made to the use of a single phenol of eachparticular type, or a single aldehyde, or a single oxyalkylating agent.Obviously, mixtures of reactants ma be employed, as, for example, amixture of cardanol and hydrogenated cardanol, or a. mixture of phenoland metacresol, or a mixture of amylphenol and butylphenol. It isextremely difiicult to depict the structure of a resin made from asingle difunctional phenol, as, for example, from para-amylphenol andformaldehyde. When a mixture of phenols is used, and this isparticularly true when such mixtures are selected exclusively fromtrifunctional phenols having a long chain substituent in the metaposition, or at least include a considerable amount of such phenol, oneruns into even greater complexity of structure.

If a mixture of aldehydes is employed, for instance, acetaldehyde andbutyraldehyde, or acetaldehyde and formaldehyde, or benzaldehyde andacetaldehyde, the final structure of the resin becomes even morecomplicated and possibly depends on the relative reactivity of thealdehydes. For that matter, one might be producing simultaneously twodifferent resins in what would actually be a mechanical mixture,although such mixture might exhibit some unique properties, as comparedwith a mixture of the same two resins prepared separately. Similarly, ashas been suggested, one might use a combination of oxyalkylating agents;for instance, one might partially oxyalkylate with ethylene oxide'andthen finish off with propylene oxide. It is understood that the use ofoxyalkylated derivatives of such resins, derived from such plurality ofreactants instead of being limited to a single reactant from each of thethree classes, is contemplated and here included, for the reason thatthey are obvious variants.

Having obtained a suitable resin of the kind described, such resin issubjected to treatment with a low molal reactive alpha-beta olefineoxide so as to render the product distinctly hydrophile in nature, asindicated by the fact that it becomes self-emulsifiable or miscible orsoluble in water, or self-dispersible, or has emulsifying properties.The olefine oxides employed are characterized by the fact, that theycontain not over 4 carbon atoms and are selected from the classconsisting of ethylene oxide, propylene oxide, butylene oxide, glycide,and methylglycide. Glycide may be, of course, considered as a hydroxypropylene oxide and methyl glycide as a hydroxy butylene oxide. In anyevent, however, all such reactants contain the reactive ethylene oxidering and may be best considered as derivatives of or substitutedethylene oxides. The solubilizing effect of the oxide is directlyproportional to the percentage of oxygen present, or specifically, tothe oxygen-carbon ratio.

In ethylene oxide, the oxygen-carbon ratio is 1:2. In glycide, it is2:3, and in methyl glycide, 1 :2. In such compounds, the ratio is veryfavorable to the production of hydrophile or surfaceactive properties.However, the ratio, in propylene oxide, is 1:3, and in butylene oxide,1:4. Obviously, such latter two reactants are satisfactorily employedonly where the resin composition is such as to make incorporationof thedesired property practical. In other cases, they may produce marginallysatisfactory derivatives, or even unsatisfactory derivatives. They areusable in conjunction with the three more favorable alkylene oxides inall cases. For'instance, after one or several propylene oxide orbutylene oxide molecules have been attached to the resin molecule,oxyalkylation may be satisfactorily continued using the more favorablemembers of the class, to produce the desired hydrophile product. Usedalone, these two reagents may in somecases fail to produce sufficientlyhydrophile derivatives because of their relatively low oxygen-carbonratios.

Thus, ethylene oxide is much more effective than propylene oxide, andpropylene oxide is more 30 effective than butylene oxide. Hydroxypropylene oxide (glycide) is more effective than propylene oxide.Similarly, hydroxy butylene oxide (methyl glycide) is more effectivethan butylene oxide. Since ethylene oxide is the cheapest alkylene oxideavailable and is reactive, its use is definitely advantageous, andespecially in light of its high oxygen content. Propylene oxide is lessreactive than ethylene oxide, and butylene oxide is definitely lessreactive than propylene oxide. On the other hand, glycide may react withalmost explosive violence and must be handled with 'ex- 7 treme care.

The oxyalkylation of resins of the kind from which the products used inthe practice of the present invention are prepared is advantageouslycatalyzed by the presence of an alkali. Useful alkaline catalystsinclude soaps, sodium acetate, sodium hydroxide, sodium methylate,caustic potash, etc. The amount of alkaline catalyst usually 3 isbetween 0.2% to 2%. The temperature. em-.

ployed may vary from room temperature to as high as 200 C. The reactionmay beconducted with or without pressure, i. e., from zero pressure toapproximately 200 oreven 300 pounds gauge pressure (pounds per squareinch); In a general.

way, the method employed is substantially the same procedure as usedforoxyalkylation of other organic materials having'reactive phenolicgoups.

It may be necessary to allow for the acidity of a resin in determiningthe amount of alkaline catalyst to be added in oxyalkylation. .For in-.

stance, if a nonvolatile strongacid such as sulfuric acid is used tocatalyze the resinification reaction, presumably after being convertedinto a sulfonic acid, it may be necessary and is usually advantageous toadd an amount of alkali equal stoichiometrically to such acidity, andinclude added alkali over and above this amount as the with many resins,the oxyalkylation proceeds satisfactorily without a solvent. 2, incexylene is cheap and may be permitted to be present in the final productused asa ,demulsifler, it is our J preference to use xylene. This isparticularly true,

in the manufacture of productsfromYlow-stage resins, i. e., of 3 and upto and including '7 units per molecule.

If a xylene solution is used in an autoclave as hereinafter indicated,the pressure readings of course represent total pressure, that is, thecombined pressure due to xylene and also due to ethylene oxide orwhatever other oxyalkylating agent is used. Under such circumstances itmay be necessary at times to use substantial pressures to obtaineffective results, for instance, pressures up to 300 pounds along withcorrespondingly high temperatures, if required.

However, even in the instance of high-melting resins, a solventsuch asxylene can be eliminated in either one of two ways: After theintroduction of approximately 2 or 3 moles of ethyleneo-xide, forexample, per phenolic nucleus, there is a definite drop in the hardnessand melting point of the resin. At this stage, if xylene or a'similarsolvent has been added, it can be eliminated by distillation (vacuumdistillation if desired) and the subsequent intermediate, beingcomparatively soft and solvent-free, can be reacted further in the usualmanner with ethylene oxide or some other suitable reactant.

Another procedure is to continue the reaction to completion with suchsolvent present and then eliminate the solvent by distillation in thecustomary manner.

Another suitable procedure is to use propylene oxide or butylene oxideas a solvent as well asa reactant in the earlier stages along withethylene oxide, for instance, by dissolving the powdered resin inpropylene oxide even though oxyalkylation is taking place to a greateror lesser degree. After a solution has been obtained which representsthe original resin dissolved in propylene oxide or butylene oxide, or amixture which includes the oxyalkylated product, ethylene oxide is addedto react with the liquid mass until hydrophile properties are obtained.Since ethylene oxide is more reactive than propylene oxide or butyleneoxide, the final product may contain some unreacted propylene oxide orbutylene oxide which can be eliminated by volatilizatio-n ordistillation in any suitable manner.

Attention is directed to the fact that the resins herein described mustbe fusible or soluble in an organic solvent. Fusible resins invariablyare soluble in one or more organic solvents such as those mentionedelsewhere herein. It is to be emphasized, however, that the organicsolvent employed to indicate or assure that the resin meets thisrequirement need not be the one used in oxyalkylation. Indeed solventswhich are susceptible to oxyalkylation are included in this group oforganic solvents. Examples of such solvents are alcohols andalcohol-ethers. However, where a resin is soluble in an organic solvent,there are usually available other organic solvents which are notsusceptible to oxyalkylation, useful for the oxyalkylation step. In anyevent, the organic solvent-soluble resin can be finely powdered, forinstance to 100 to 200 mesh, and a slurry, or suspension prepared inxylene or the like, and subjected to oxyalkylation. The fact that theresin is soluble in an organic solvent or the fact that it is fusiblemeans that it consists of separate molecules. Phenol-aldehyde resins ofthe type herein specified possess reactive hydroxyl groups and areoxyalkylation susceptible.

Considerable of what is said immediately hereinafter is concerned withthe ability to vary the hydrophile properties of the compounds used inthe process from minimum hydrophile properties to maximum hydrophileproperties. Even more remarkable, and equally dificult to explain, arethe versatility and utility of these compounds as one goes from nimiumhydrophile property to ultimate maximum hydrophile property. Forinstance, minimum hydrophile property may be described roughly as thepoint where two ethyleneoxy radicals or moderately in excess thereof areintroduced per phenolic hydroxyl. Such minimum hydrophile property ofsub-surface-activity or minimum surface-activity means that the productshows at least emulsifying properties or self-dispersion in cold or evenin warm distilled water to 40 C.) in concentrations of 0.5% to 5.0%.These materials are generally more soluble in cold water than warmwater, and may even be very insoluble in boiling water. Moderately hightemperatures aid in reducing the viscosity of the solute underexamination. Sometimes if one continues to shake a hot solution, eventhough cloudy or containing an insoluble phase, one finds that solutiontakes place to give a homogeneous phase as the mixture cools. Suchself-dispersion tests are conducted in the absence of an insolublesolvent.

When the hydrophile-hydrophobe balance is above the indicated minimum (2moles of ethylene oxide per phenolic nucleus or the equivalent) butinsufiicent to give a sol as described immediately preceding, then, andin that event hydrophile properties are indicated by the fact that onecan produce an emulsion by having present 10% to 50% of an inert solventsuch as xylene. All that one need to do is to have a xylene solutionwithin the range of 50 to parts by weight of oxyalkylated derivativesand 50 to 10 parts by weight of xylene and mix such solution with one,two or three times its volume of distilled water and shake vigorously soas to obtain an emulsion which may be of the oil-in-water type or thewater-in-oil type (usually the former) but, in any event, is due to thehydrophile-hydrophobe balance of the oxyalkylated derivative. We prefersimply to use the xylene diluted derivatives, which are describedelsewhere, for this test rather than evaporate the solvent and employany more elaborate tests, if the solubility is not sufiicient to permitthe simple sol test in water previously noted.

If the product is not readily water soluble it may be dissolved in ethylor methyl alcohol, ethylene glycol diethylether, or diethylene glycoldiethylether, with a little acetone added if required, making a ratherconcentrated solution, for instance 40% to 50%, and then adding enoughof the concentrated alcoholic or equivalent solution to give thepreviously suggested 0.5% to 5.0% strength solution. If the product isself-dispersing (i. e., if the oxyalkylated product is a liquid or aliquid solution self-emulsifiable), such sol or dispersion is referredto as at least semi-stable in the sense that sols, emulsions, ordispersions prepared are relatively stable, if they remain at least forsome period of time, for instance 30 minutes to two hours, beforeshowing any marked separation. Such tests are conducted at roomtemperature (22 C.) Needless to say, a test can be made in presence ofan insoluble solvent such as 5% to 15% of xylene, as noted in previousexamples. If such mixture, i. e., containing a water-insoluble solvent,is at least semi-stable, obviously the solvent-free product would beeven more so. Surface-activity representin an advancedhydrophile-hydrophobe balance can also be determined by the use ofconventional measurements hereinafter described. One outstandingcharacteristic property indicating surfaceactivity in a material is theability to form a permanent foam in dilute aqueous solution, forexample, less than 0.5%, when in the higher oxyalkylated stage, and toform an emulsion in the lower and intermediate stages of oxya-lkylation.

Allowance must be made for the presence of a solvent in the finalproduct in relation to the hydrophile properties of the final product.The principle involved in the manufacture of the herein contemplatedcompounds for use as demulsifyin agents, is based on the conversion of ahydrophobe or non-hydrophile compound or mixture of compounds intoproducts which are distinctly hydrophile, at least to the extent thatthey have emulsifying properties or are selfemulsifying; that is, whenshaken with water they produce stable or semi-stable suspensions, or, inthe presence of a water-insoluble solvent, such as xylene, an emulsion.In demulsification, it is sometimes preferable to use a product havingmarkedly enhanced hydrophile properties over and above the initial stageof self-emulsifiability, although we have found that with products ofthe type used herein, most efficacious results are obtained withproducts which do not have hydrophile properties beyond the stage ofself-dispersibility.

More highly oxyalkylated resins give colloidal solutions or sols whichshow typical properties comparable to ordinary surface-active agents.Such conventional surface-activity may be measured by determining thesurface tension and the interfacial tension against parafiin oil or thelike. At the initial and lower stages of oxyalkylation, surface-activityis not suitably determined in this same manner, but one may employ anemulsification test. Emulsions come into existence, as a rule, throughthe presence of a surface-active emulsifying agent. Some surface-activeemulsifying agents such as mahogany soap may produce a water-in-oilemulsion, or an oil-in-water emulsion, depending upon the ratio of thetwo phases, degree of agitation, concentration of emulsifyin agent, etc.

The same is true in regard to the oxyalkylated resins herein specified,particularly in the lower stage of oxyalkylation, the so-calledsub-surface-active stage. The surface-active properties are readilydemonstrated by producing a xylene-water emulsion. A suitable procedureis as follows: The oxyalkylated resin is dissolved in an equal weight ofxylene. Such 50-50 solution is then mixed with 1-3 volumes of water andshaken to produce an emulsion. The amount of xylene is invariablysufficient to reduce even a tacky resinous product to a solution whichis readily dispersible. The emulsions so produced are usuallyxylene-in-water emulsions (oil-inwater type) particularly when theamount of distilled water used is at least slightly in excess of thevolume of xylene solution and also if shaken vigorously. At times,particularly in the lowest stage of oxyalkylation, one may obtain awaterin-xylene emulsion (water-in-oil type), which is apt to reverse onmore vigorous shaking and further dilution with water.

If in doubt as to this property, comparison with a resin obtained frompara-tertiary butylphenol and formaldehyde (ratio 1 part phenol to 1.1formaldehyde) using an acid catalyst and then followed by oxyalkylation,using 2 moles of ethylene oxide for each phenolic hydroxyl, is helpful.

The procedure followed in preparing such a standard resin for comparisonwas the same procedure as described in Example 1*, preceding. A specificexample of ingredients suitable for making such resin is as follows:

Grams Para-tertiary butylphenol (1.0 mole) 150 Formaldehyde (37%) (1.1mole) 90 Concentrated HCl 1.5

Monoalkyl (C1oC2o, principally C1z-C14) benzene monosulfonic acid sodiumsalt" 0.8 Xylene 100 Such resin, prior to oxyalkylation, has a molecularweight indicating about 4 /2 units per resin molecule. Such resin, whendiluted with an equal weight of xylene, will serve to illustrate theabove emulsification test.

In a few instances, the resin may not be sufficiently soluble in xylenealone, but may require the addition of some ethylene glycoldiethylether, as described elsewhere. It is understood that suchmixture, or any other similar mixture, is considered the equivalent ofxylene for the purpose of this test.

In many cases, there is no doubt as to the presence or absence ofhydrophile or surfaceactive characteristics in the products used inaccordance with this invention. They dissolve or disperse in water; andsuch dispersions foam readily. With borderline cases, i. e., those whichshow only incipient hydrophile or surface-active property(sub-surface-activity) tests for emulsifying properties orself-dispersibility are useful. The fact that a reagent is capable ofproducing a dispersion in water is proof that it is distinctlyhydrophile. In doubtful cases, comparison can be made with thebutylphenol-formaldehyde resin analog wherein 2 moles of ethylene oxidehave been introduced for each phenolic nucleus.

The presence of xylene or an equivalent waterinsoluble solvent may maskthe point at which a solvent-free product on mere dilution in a testtube exhibits self-emulsification. For this reason, if it is desirableto determine the approximate point where self-emulsification begins,then it is better to eliminate the xylene or equivalent from a smallportion of the reaction mixture and test such portion. In some cases,such xylene-free resultant may show initial or incipient hydrophileproperties, whereas in presence of xylene such properties would not benoted. In other cases, the first objective indication of hydrophileproperties may be the capacity of the material to emulsify an insolublesolvent such as xylene. It is to be emphasized that hydrophileproperties herein referred to are such as those exhibited byincipientself-emulsification or the presence of emulsifying properties and gothrough the range of homogeneous dispersibility or admixture with watereven in the presence of added water-insoluble solvent and minorproportions of common electrolytes as occur in oil field brines.

Elsewhere, it is pointed out that an emulsification test may be used todetermine ranges of surface-activity and that such emulsification testsemploy a xylene solution. Stated another way, it is really immaterialwhether a xylene solution produces a sol or whether it merely producesan emulsion.

In light of what has been said previously in regard to the variation ofrange of hydrophile properties, and also in light 'of what has been saidas to the variation in the effectiveness of various alkylene oxides, andmost particularly of all ethyltained-varies somewhat with the conditionsof reaction, the proportions of reactants, the nature of the catalyst,etc.

Based on molecular weight determinations, most of the resins prepared asherein described, particularly in the absence of a secondary heatingstep, contain 3 to 6 or '7 phenolic nuclei with approximately 4 or 5nuclei as an average. More drastic conditions of resinification yieldresins of greater chain length. Such more intensive resinification is aconventional procedure and may be employed if desired. Molecular weight,of course, is measured by any suitable procedure, particularly bycryoscopic methods; but using the same reactants and using more drasticconditions of resinification one usually finds that higher moeiularweights are indicated by higher melting points of the resins and atendency to decreased solubility. See what has been said elsewhereherein in regard to a secondary step involving the heating of a resinwith or without the use of vacuum.

We have previously pointed out that either an alkaline or acid catalystis advantageously used in preparing the resin. A combination ofcatalysts is sometimes used in two stages; for instance, an alkalinecatalyst is sometimes employed in a first stage, followed byneutralization and addition of a small amount of acid catalyst in asecond stage. It is generally believed that even in the presence of analkaline catalyst, the number of moles of aldehyde, such asformaldehyde, must be greater than the moles of phenol employed in orderto introduce methylol groups in the intermediate stage. There is noindication that such groups appear in the final resin if prepared by theuse of an acid catalyst. It is possible that such groups may appear inthe finished resins prepared solely with an alkaline catalyst; but wehave never been able to confirm this fact in an examination of a largenumber of resins prepared by ourselves. Our preference, however, is touse an acid-catalyzed resin, particularly employing aformaldehyde-to-phenol ratio of 0.95 to 1.20 and, as far as we have beenable to determine, such resins are free from methylol groups. As a materof fact, it is probable that in acid-catalyzed resinifications. themethylol structure may appear only momentarily at the very beginning ofthe reaction and in all probability is converted at once into a morecomplex structure during the intermediate stage.

One procedure which can be employed in the use of a new resin to preparepro-ducts for use in the process of the invention is to determine thehydroxyl value by the Verley-Bdlsing method or its equivalent. Theresin, as such, or in the form of a solution, as described, is thentreated with ethylene oxide in presence of 0.5% to 2% of sodiummethylate as a catalyst in step-wise fashion. The conditions ofreaction, as far as time or percent are concerned, are within the rangepreviously indicated. With suitable agitation, the ethylene oxide, ifadded in molecular proportion, combines within a comparatively shorttime, for instance. a few minutes to '2 to 6 hours, but in someinstance, requires as much as 8 to 24 hours. A useful temperature rangeis from 125 to 225 C. The completion of the reaction of each addition ofethylene oxide in stepwise fashion is usually indicated by the reductionor elimination of pressure. An amount conveniently used for eachaddition is generally equivalent to a mole or two moles of ethyleneoxide per hydroxyl radical. When the amount of ethylene oxide added isequivalent to approximately 50%, by weight, of the original resin, asample is tested for incipient hydrophile properties, by simply Shakingup in water as is, or after the elimination of the solvent, if a solventis present. The amount of ethylene oxide used to obtain a usefuldemulsifying agent. as a rule, varies from 70%, by weight, of theoriginal resin to as much as five or six times the weight of theoriginal resin. In the case of a resin derived from para-tertiarybutylphenol and cardanol, or cardanol in combination with para-cresol,or in combination with metacresol, or in combination with both meta andpara-cresol, as little as 50%, by weight, of ethylene oxide may givesuitable solubility. With propylene oxide, even a greater molecularproportion is required and sometimes a resultant of only limitedhydrophile properties is obtainable. The same is true to even a greaterextent with butylene oxide. The hydroxylated alkylene oxides are moreeifective in solubilizing properties than the comparable compounds inwhich no hydroxyl is present.

Attention is directed to the fact that in the subsequent examplesreference is made to the step-wise addition of the alkylene oxide, suchas ethylene oxide. It is understood, of course, there is no objection tothe continuous addition of alkylene oxide until the desired stage ofreaction is reached. In fact, there may be less of a hazard involved andit is often advantageous to add the alkylene oxide slowly in acontinuous stream and in such amount as to avoid exceeding the higherpressures noted in the various examples or elsewhere.

It may be well to emphasize the fact that when resins are produced fromdifunctional phenols and some of the higher aliphatic aldehydes, such asacetaldehyde, the resultant is a comparatively soft or pitch-like resinat ordinary temperatures. Such resins become comparatively fluid at toC. as a rule, and thus can be readily oxyalkylated, preferablyoxyethylated, without the use of a solvent.

What has been said previously is not intended to suggest that anyexperimentation is necessary to determine the degree of oxyalkylation,and particularly oxyethylation. What has been said previously issubmitted primarily to emphasize the fact that these remarkableoxyalkylated resins having surface activity show unusual properties asthe hydrophile character varies from a minimum to an ultimate maximum.One should not underestimate the utility of any of these products in asurface-active or sub-surface-active range without testing them fordemulsification. A few simple laboratory tests which can be conducted ina routine manner will usually give all the information that is required.

For instance, a simple rule to follow is to prepare a resin having atleast three phenolic nuclei and being organic solvent-soluble.Oxyethylate such resin, using the following four ratios of moles ofethylene oxide per phenolic unit equivalent: 2 to l; 6 to 1; 10 to l;and 15 to 1. From a sample of each product remove any solvent that maybe present, such as xylene. Prepare 0.5% and 5.0% solutions in distilledwater, as previously indicated. A mere examination of such series willgenerally reveal an approximate range of minimum hydrophile character,moderate hydrophile character, and maximum hydrophile character. If the2 to 1 ratio does not show minimum hydrophile character by test of thesolventfree product, then one should test its capacity to form anemulsion when admixed with xylene or other insoluble solvent. If neithertest shows the required minimum hydrophile property, repetition using 2to 4 moles per phenolic nucleus will serve. Moderate hydrophilecharacter should be shown by either the 6 to 1 or 10 to 1 ratio. Suchmoderate hydrophile character is indicated by the fact that the sol indistilled water within the previously mentioned concentration range is apermanent translucent sol when viewed in a comparatively thin layer, forinstance, the depth of a test tube. Ultimate hydrophile character isusually shown at the 15 to 1 ratio test, in that adding a small amountof an insoluble solvent, for instance, 5% of xylene, yields a productwhich will give, at least temporarily, a transparent or translucent solof the kind just described. The formation of a permanent foam, when a0.5% to 5.0% aqueous solution is shaken, is an excellent test forsurface activity. Previous reference has been made to the fact thatother oxyalkylating agents may require the use of increased amounts ofalkylene oxide. However, if one does not even care to go to the troubleof calculating molecular weights, one can simply arbitrarily preparecompounds containing ethylene oxide equivalent to about 50% to 75%, byweight, for example, 65%, by weight, of the resin to be oxyethylated; asecond example using approximately 200% to 300%, by weight, and a thirdexample, using about 500% to 750%, by weight, to explore the range ofhydrophile-hydrophobe balance.

A practical examination of the factor of oxyalkylation level can be madeby a very simple test, using a pilot plant autoclav having a capacity ofabout to gallons, as hereinafter described. Such laboratory-preparedroutine compounds can then be tested for solubility, and, generallyspeaking, this is all that is required to give a suitable varietycovering the hydrophilehydrophobe range. All these tests, as stated, areintended to be routine tests and nothing more. They are intended toteach a person, even though unskilled in oxyethylation or oxyalkylation,how to prepare in a perfectly arbitrary manner, a series of compoundsillustrating the hydophilehydophobe range.

Ordinarily, the oxyalkylation is carried out in autoclaves provided withagitators or stirring devices. We have found that the speed of theagitation markedly influences the time of reaction. In some cases, thechange from slow speed agitation, for example, in a laboratory autoclaveagitation with a stirrer operating at a speed of 60 to 200 R. P. M. tohigh speed agitation, with the stirrer operating at 250 to 350 R. P. M.,reduces the time required for oxyalkylation by about one-half totwo-thirds. Frequently xylene-soluble products which give insolubleproducts by procedures employing comparatively slow speed agitation givesuitable hydrophile products when produced by similar procedure, butwith high speed agitation, as a result, we believe of the reduction inthe time required with consequent elimination or curtailment ofopportunity for ouring or etherization. Even if the formation of aninsoluble product is not involved, it is frequently advantageous tospeed up the reaction, thereby reducing production time, by increasingagitating speed. In large scale operations we have demonstrated thateconomical manufacturing results from continuous oxyalkylation, i. e.,an operation in which the alkylene oxide is continuously fed to thereaction vessel, with high speed agitation, i. e., an agitator operatingat 250 to 350 R. P. M.

Continuous oxyalkylation, other conditions being the same, is more rapidthan batch oxyalkylation, but the latter is ordinarily more convenientfor laboratory operation.

As far as we know, some thermoplastic or fusible cardanol or mixedcardanol resins are offered in the open market for purposes other thanthose herein described. If one obtains such a resin, one might have tomake certain determinations, in order to make the quickest approach tothe appropriate oxyalkylation range. For instance, one should know (a)the molecular size,.indicating the number of phenolic units; (1)) thenature of the aldehydic residue, which is usually CHzj and (c) thenature of the substituent, which may be a cardanol type resin alone or ahydrogenated may be employed that it is somewhat difficult to calculatea molecular weight, except as a statistical average. If, on the otherhand, a resin is obtained from a single phenol, such as cardanol, thenthe molecular weight of the internal structural units of the resin ofthe following oversimplified formula:

(n=1 to 13, or even more) is given approximately by the formula: (mol.wt. of phenol 2) plus mol. wt. of methylene or substituted methyleneradical. The molecular weight of the resin would be n times the valuefor the internal limit plus the values for the terminal units. Theleft-hand terminal unit ofthe above structural formula, it will be seen,is identical with the recurring internal unit, except that it has oneextra hydrogen. The right-hand terminal unit lacks the methylene bridgeelement- Using one internal unit of a resin as the'basic element, aresins molecular weight is given approximately by taking (n plus 2)times the weight of the internal element. Where the resin .molecule hasonly 3 phenolic nuclei, as in the structure show'n,,th is calculationwill'be in error by several percent, but as it grows larger, to contain6, 9, or 12 phenolic nuclei, the formula comes to be more thansatisfactory. Using such an approximate weight, one need only introduce,for example, two molal weights of ethylene oxide or slightly more, perphenolic nucleus, 'to produce a product of minimal hydrophile character.

character. Although we have prepared and tested a large numberofoxyethylated products of the type described herein, we have found noinstance where the use of less than'2 moles of ethylene oxide perphenolicnucleus gave desirable products. r

The following examples, 1 through9 are included to exemplify theproduction of oxyalkylation products of the invention from re'sins,specifically, resins described in nine of the foregoing Examples 1 to 82giving exact and, complete details for the carrying out of theprocedure. In the table which appears further on in the specificationaregiven data with respect to the oxyethylation of a number of theresins previously described, it being understoodthat in preparing v theproducts referred to in the table, themanipulative steps used are-thoseof Examples 1 to 9 EXAMPLE l Further oxyalkylation gives enhancedhydrophile.

Itf

to wit, powdered sodium methylate. The amount of sodium methylateemployed was 2.6% based on the weight of the solvent-free resin. Thismixture, to Wit, the resin, xylene and the sodium methylate powder, isplaced in an autoclave and approximately 5850 grams of ethylene oxideadd in six portions of 900 grams in the first five, and 1350 in the lastaddition. After each portion is added, the reaction is allowed to takeplace until it is complete, as indicated by the drop in pressure to thatof the solvent alone. This particular resin seemed to be particularlysusceptible to oxyethylation, and in each case, the addition of ethyleneoxide was made in less than an hour, usually requiring minutes to thirtyminutes. The temperature employed varied from approximately 113 to 155C. The gauge ressure stayed low on the first four additions, i. e., itvaried from 50 pounds to 80 pounds per square inch. On the fifthaddition, the gauge pressure became rather high, rising to 250 pounds.On the last addition it was low again, back to 50 pounds. Tests weremade on the solubilit of the oxyethylated product as oxyethylationproceeded. The product at the end of the sixth addition was completelywater-soluble. Reference is made to the hereto appended table, where allthese data are tabulated. This indicated that incipient emulsificationin absence of xylene may have appeared at an earlier stage, forinstance, at the fifth addition, or possibly even at the fourthaddition. The original amount of resin employed, 4200 grams, wasrendered water-soluble when an equal weight of ethylene oxide was added,and possibly fairly soluble when, at the end of the fourth addition,3600 grams of ethylene oxide were added. As previousl pointed out, amore exact evaluation is possible, if the xylene or other solvent isremoved. The final product, when cold, was a somewhat viscous liquid,reddish-amber in color, and as stated, was emulsifiable in water, evenin the presence of added xylene.

EXAMPLE 2 The same reactants, and procedure, were employed as in Example1*, preceding, except that propylene oxide was employed instead ofethylene oxide. The resultant, even on the addition of the alkyleneoxide in the weight proportions of the revious example, has diminishedhydrophile properties, in comparison with the resultants of Example 1*.This illustrates the point that propylene oxide and butylene oxide giveproducts of lower levels of hydrophile properties than does ethyleneoxide.

EXAMPLE 3 The same reactants and procedure were followed as in Example 1except that one mole of glycide was employed initially per hydroxyradical. This particular reaction was conducted with extreme care andthe glycide was added in small amounts representing fractions of a mole.Ethylene oxide was then added, following the procedure of Example 1, toproduce products of greater hydrophile properties. We are extremelyhesitant to suggest even the experimental use of ly e nd m ylly for thereason that disastrous results may be obtained even in experimentationwith laboratory quantities.

EXAMPLE 4 The same procedure was followed as in Example 1 except thatinstead of employing the resin used in Example 1 there was used instead40 the cardanol formaldehyde resin obtained by means of an alkalinecatalyst (ammonia) as described under the heading of Example 2 EXAMPLE 5The procedure employed was the same as that in Example l except thatinstead of using the resin described under the heading Example 1*, therewas employed instead the resin described under the heading Example 3This particular resin was obtained from cardanol and acetaldehyde,employing concentrated sulfuric acid as a catalyst. As to the details ofthe oxyethylation procedure, see the hereto appended table.

EXAMPLE 6 The same procedure was employed as in Example l preceding,except that the resin employed was the particular one described underthe heading of Example 16 This resin was derived from cardanol incombination with phenol. It was a formaldehyde resin obtained by meansof an acid catalyst. The details of oxyethylation are set forth in asubsequent table.

EXAlWPLE 7 The procedure followed was the same as in Example 1preceding, but the resin employed was one derived from cardanol and adifunctional phenol, to wit, a difunctional cresol. The resin was theone described under the heading of Example 37. The details ofoxyethylation appear in the table.

EXAMPLE 8* The procedure followed was the same as in Example lpreceding. The resin employed was a resin obtained from cardanol incombination with both a difunctional phenol and a, trifunctional phenol.The specific resin was that described under the heading of Example 62*.As to details of oxyethylation, see the hereto appended table.

EXAMPLE 9 The same procedure was followed as in Example 1 preceding. Theparticular resin employed was one obtained from cardanol in combinationwith both a difunctional phenol and a trifunctional phenol, butemploying acetaldehyde instead of formaldehyde. The particular resin isobtained under the heading of Example 66 As to details of oxyethylation,see the table that follows.

Our experience with chlorinated reactants during oxyalkylation,particularly oxyethylation, is that an alkaline catalyst is not apt tobe satisfactory if the chlorine shows any liability at all. This isusually the case, and, as a result, the alkaline catalyst is convertedinto sodium chloride with the corresponding change in the organicreactant. In such instances, we prefer to use the type of reactantemployed in a Friedel- Crafts reaction. Such catalyst is an acid in someof the common systems of acid based nomenclature. Examples includealuminum chloride, ferric chloride, stannic chloride, etc. In theoxyethylation of Examples 10 29 46 and 74, as previously described, anddescribed in further detail in the subsequent table, tin tetrachloridewas used instead of sodium methylate.

The resins, prior to oxyethylation, vary from tacky resins having asuggestion of hardness, to tacky viscous liquids. Their color variesfrom a reddish-amber to a blackish-amber, particularly in the latterdirection when the amount of cardanol or cardanol derivative increases.In the

1. A PROCESS FOR BREAKING PETROLEUM EMULSIONS OF THE WATER-IN-OIL TYPE,CHARACTERIZED BY SUBJECTING THE EMULSION TO THE ACTION OF A DEMULSIFYINGAGENT INCLUDING HYDROPHILE SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETICPRODUCTS BEING OXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENEOXIDE HAVING NOT MORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASSCONSISTING OF ETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDEAND METHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE,ORGANIC-SOLVENT-SOLUBLE, WATERINSOLUBLE PHENOL-ALDEHYDE RESIN; SAIDRESIN BEING DERIVED BY REACTION BETWEEN AN ANACARDIC ACID PHENOLREACTANT AND AN ALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND REACTIVETOWARDS SAID PHENOLIC REACTANT; SAID OLYALKYLATED RESIN BEINGCHARACTERIZED BY THE INTRODUCTION INTO THE RESIN MOLECULE OF A PLURALITYOF DIVALENT RADICALS HAVING THE FORUMLA (R1O)N IN WHICH R1 IS A MEMBERSELECTED FROM THE CLASS CONSISTING OF ETHYLENE RADICALS, PROPYLENERADICALS, BUTYLENE RADICALS, HYDROXYPROPYLENE RADICALS, AND N IS ANUMERAL VARYING FROM 1 TO 20; WITH THE PROVISO THAT AT LEAST 2 MOLES OFALKYLENE OXIDE BE INTRODUCED FOR EACH PHENOLIC NUCLEUS; SAID ANACARDICACID PHENOLIC REACTANT BEING DERIVED FROM THE CLASS CONSISTING OF (A) ANANACARDIC ACID PHENOL AND THE SIDE CHAIN CHLORINATED AND THE SIDE CHAINHYDROGENATED DERIVATIVES THEREOF; (B) A MINOR PROPORTION OF THETRIFUNCITONAL PHENOL FREE FROM ANY META SUBSTITUENT HAVING MORE THAN 4CARBON ATOMS IN ADMIXTURE WITH A MAJOR PROPORTION OF THE ANACARDIC ACIDPHENOL SPECIFIED IN (A) PRECEDING; (C) A DIFUNCTIONAL PHENOL INADMIXTURE WITH AN ANACARDIC ACID PHENOL DESCRIBED IN (A) PRECEDING INSUCH PROPORTIONS THAT THERE IS AT LEAST ONE NUCLEUS FROM EACH TYPE OFPHENOL PER RESIN MOLECULE; AND (D) A MAJOR PROPORTION OF A MIXTURE OF(C) PRECEDING, IN COMBINATION WITH A MINOR PROPORTION OF A TRIFUNCTIONALPHENOL FREE FROM ANY META POSITION SUBSTITUENT HAVING MORE THAN 4 CARBONATOMS THE PROPORTIONS BEING SUCH THAT THERE IS AT LEAST ONE ANACARDICACID PHENOL NUCLEUS PER RESIN MOLECULE.